AU658150B2

AU658150B2 - Improved formulations

Info

Publication number: AU658150B2
Application number: AU85546/91A
Authority: AU
Inventors: Masuo Kuchikata; Tatsuo Sato
Original assignee: Monsanto Co
Current assignee: Monsanto Technology LLC
Priority date: 1990-10-04
Filing date: 1991-10-03
Publication date: 1995-04-06
Anticipated expiration: 2011-10-03
Also published as: MY109373A; EP0483095A2; AU8554691A; NZ240081A; EP0483095A3

Description

COMMONWEALTH OF AUSTRALIA PATENTS ACT 1990 58150 REGULATION 3.2 39-21(2579)A AS Name of Applicant: Actual Inventor/s: Address for Service: 0 0 S S egee

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5 0 5 00 0 5 0 MONSANTO COMPANY MASUO KUCHIKATA TATSUO SATO E.F. WELLINGTON CO., Patent and Trade Mark Attorneys, 312 St. Kilda Road, Melbourne, 3004, Victoria.

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Invention Title: "IMPROVED FORMULATIONS" Details of Associated Provisional Applications Nos: The following statement is a full description of this invention including the best method of performing it known to us.

1 -1A- 0 9 2 l(2579)A Field of the Invention This invention relates to a storage stable aqueous formulation containing glyphosate herbicide having enhanced stability properties, to a process for preparin such compositions, and to a herbicidal method of use of such compositions.

Description of the Prior Art N-phosphonomethylglycine, whose common name is glyphosate, is well known in the art as a highly effective herbicide. It is also known that glyphosate, an organic acid, has a low solubility in water.

Glyphosate is typically formulated as a water-soluble salt, especially as the mono-isopropylamine (IPA) salt to kill or control weeds or plants. Glyphosate is S 15 typically sold commercially as an aqueous concentrate in the form of its IPA salt by Monsanto Company under the .1 trademark Roundup.

Various salts of glyphosate, methods for preparing such salts of glyphosate, formulations of glyphosate and methods of use for killing and controlling weeds and plants are disclosed in U.S.

Patents 3,799,758 and 4,405,531 issued to John E. Franz on March 26, 1974 and September 20, 1983, respectively.

Other U.S. Patents which disclose salts of glyphosate 25 include US 4,315,765 issued to George B. Large on February 16, 1982, US 4,507,250 issued to Izhak Bakel on March 26, 1985, US 4,397,676 issued

J

.i Izhak Bakel on August 9, 1983, US Patent 4,481,026 issued to Michael P.

Prisbylla on November 6, 1984 and, US 4,140,513 issued to Erhard J. Prill on February 20, 1979. The aforementioned patents are incorporated herein in their entireties by reference thereto.

-2- 09-21(2579)A The use of an organosilicone surfactant, such as Silwet® L-77 sold by Union Carbide Company, in tank mixes with commercially purchased Roundup herbicide improves the rainfastness of the resulting tank mix with Roundup on some species of weeds.

Monsanto sells Pulse brand penetrant (which is Silwet® L-77) for tank mix use with Roundup herbicide.

The label of Pulse penetrant discloses that the addition of Pulse penetrant can reduce the rainfree period after application of Roundup herbicide for best activity from 4-6 hours to 2 hours on perennial ryegrass when recommended rates of Roundup herbicide and Pulse penetrant are sprayed on dry foliage.

L. Janzen, "Enhancement of Herbicides by Silicone Surfactants" Volume 21, Issue 2 (March) 1983, WEED SCIENCE, discloses that in a comparative evaluation of S- adjuvant effects in eight species, nonionic silicone 20 glycol surfactants enhanced the activity of six herbicides to a greater extent than a standard organic surfactant, whereas cationic amino silicone surfactants enhanced to a lesser extent.

25 As mentioned above, organosilicones are sold commercially under the trademark Silwet® by Union Carbide. In particularly, SILWET Surfactants L-77, L-720, L-7001, L-7500, L-7600, L-7602, L-7604, L-7605, Sand L-7607 are exempted by the Environmental Protection 30 Agency (EPA) [40 CRF 180,1001(c)] from the requirement of a residue tolerance, when used in accordance with good agricultural practice as inert ingredients in pesticide formulations applied to growing crops or to raw agricultural commodities after harvest.

Summary of the Invention There is provided a novel and useful composition containing a glyphosate based herbicide, a silicone 0 9 2 1(2579)A copolymer wetting agent and an amphoteric surfactant.

The amount of silicone based polymer wetting agent in the herbicide containing composition can be in the range from about 0.1 to about 50 by weight of the composition, preferably in the range from about 1 to about by weight of the composition.

The amount of amphoteric surfactant in the herbicide containing composition can be in the range from about 1 to about 50 by weight of the composition and preferably in the range from about 5 to about 30 by weight of the composition.

Compositions of this invention may optionally further comprise suitable at effective amounts of ammonium sulfate, potpsium sulfate, potassium chloride, sodium sulfate, urea, ammonium phosphate mixtures thereof and the like. The composition may optionally include a synergist, quick-burn additive, a humectant, a co-herbicide, a dye, pigment, corrosion inhibitor, thickener, dispersing agent, calcium sequestrant, defoamer, mixtures thereof and like additiments.

In another embodiment of this invention, the Snovel composition is prepared by admixing an agriculturally acceptable salt of N-phosphonomethylglycine with one or more amphoteric surfactant(s) and an organosilicone 30 block copolymer. The glyphosate salt preferably is the isopropylamine, ammonium salt or an alkali metal salt with sodium being the preferred alkali metal salt.

35 Ob-ects of the Invention It is an ob ect of this invention to provide a ,storage stable licuid glyphosate herbicide, a process 4 for preparing zhis zcmccsition and a herbicidal mnec.-d 09-21(2579)A of use for killing and controlling weeds by applying a herbicidally effective amount of the composition to the locus of the plant or weed to be killed or controlled.

Detailed DescriDtion of the Invention This invention comprises a storage stable glyphosate based, herbicidal composition containing an effective amount of an organosilicone wetting agent and an amphoteric surfactant.

Illustrative types of amphoteric surfactants which may be employed in this inventions include: amine oxides a) trialkylamine oxides i) lauryl dimethyl amine oxide ii) stearyl dimethyl amine oxide b) dihydroxyethyl alkyl amine oxide i) dihydroxyethyl octyl amine oxide ii) dihydroxyethyl dodecyl amine oxide iii) dihydroxyethyl tallowamine oxide c) di(polyhydroxyethylene) alkyl amine oxide i) bis(polyoxyethylene) tallowamine oxide d) loweralkyl polyoxyethylene alkyl amine oxide i) methyl polyoxyethylene (2 mole) cocoamine oxide

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0 9-21(2579)A Other.general class, subclasses and species of amine oxides, useful in the practice of the present invention will be known to those skilled in the art. Certain amine oxides will provide for more stable formulations than others and those skilled in the art will be able to readily optimize formulations of the present invention by selection of suitable amine oxides and by varying the concentrations of the formulation ingredients.

Amine oxides useful in the formulation of the present invention are commercially available from a number of manufacturers and are generally described in McCutcheon's Detergents and Emulsifiers, North American Edition 1985 Annual and in McCutcheon's Detergent and Emulsifiers International Edition 1985.

S S The formulations may optionally contain a solvent. A suitable class of solvent is polyalkylene glycol. Suitable solvents are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol or polyethyl- '2 ene-polypropylene glycol copolymer.

09-21(2579)A One preferred class of silicone wetting agent has the average formula R R R R I I I I R (I) R R R _x L _y

R

3 R 1 0(C 2

H

3

R

2 0)a(C 3

H

6 0)b where each R is independently a monovalent hydrocarbyl radical, R 1 is a divalent hydrocarbylene radical, R 2 is independently hydrogen or a lower hydroxyalkyl radical,

R

3 is hydrogen or a monovalent hydrocarbyl radical, x, y, a and b are integers independently greater than or equal to zero.

Preferably in compounds of Formula I, R and R 3 are

-CH

3 R' is -C3H6- R 2 is hydrogen, x is zero or one, y is one to five, a is five to 20 and b is zero.

Organosilicones of Formula I above is generally 25 described in the above-mentioned Union Carbide Corp.

product literature and in U.S. Pat. Nos. 3,505,377, 3,980,688, and 4,431,789, the disclosures of which are incorporated herein by reference. Several of such ethoxylated wetting agents are available form Union 30 Carbide Corp. as SILWET surface active copolymers.

S" Preferred SILWET surface active copolymers include SILWET L-77, L-7600, L-7602 and L-7607. SILWET L-77 is an especially preferred ethoxylated wetting agent. It is believed to have Formula I above, where R and R are 35 -CH3, R is -C 3

H

6

R

2 is hydrogen, x is zero or one, y is one or two, a is about seven and b is zero.

09-21(2579)A The glyphosate salt component of a compositions of this invention may be preferably prepared by admixing various bases (acid acceptors) including those selected from those listed belowwith glyphosate wetcake or moistened glyphosate, ammonium hydroxide, and alkali metal carbonates, bicarbonates, meta borates, citrates, formates, oxalates, phosphates, propionates, pyrophosphates, metasilicates, orthosilicates, sulfites, thiosulfates, tetraborate, monoacid phosphates, tripolyphosphates, metaphosphates, sodium hydroxide, potassium hydroxide, tetrasodium EDTk, mixtures thereof and the like. Mixtures of glyphosate and salts thereof may be employed as glyphosate based materials in this invention.

Preferable agriculturally acceptable salts of Nphosphonomethylglycine include the ammonium, isopropylamine, trimethylsulfonium, imminourea salts, sodium, potassium, mixtures thereof and the like. The IPA salt, sodium, potassium and ammonium salts of N-phosphonomethylglycine are especially preferred in this invention. Mixtures of water soluble salts of N-phosphonomethylglycine may be employed herein, as well as surfactant salts of N-phosphonomethylglycine including, i 25 for example, a N,N-bis(hydroxyethylcocoamine) salt of N-phosphonomethylglycine.

In another embodiment the composition of this invention further comprises ammonium sulfate, potassium sulfate, potassium chloride, sodium sulfate, urea, ammonium phosphate mixtures thereof and the like.

The salt of N-phosphonomethylglycine may be prepared by admixing an acid acceptor with N-phosphono- 35 methylglycine (containing in the range from about 10 to about 15 wt water) to neutralize the N-phosphono- AfA methylglycine. A slight excess of acid acceptor may be 09-21(2579)A preferred, (however it is not required when ammonium hydroxide or ammonium bicarbonate is the base.) When the composition of this invention includes a liquid wetting agent the process of preparation comprises admixing said water soluble, agriculturally acceptable salt of N-phosphonomethylglycine and said one or more liquid wetting agents optionally with ammonium sulfate and thereafter blending these ingredients singly or collectively to form an admixed composition as a composition of this invention.

Table 1 illustrates various storage stable (at and 60°C) formulations of this invention. Column 1 is the example number, column 2 provides the chemical name of the surfactant, following column 3 discloses the active in the surfactant, and column 4 provides the weight ratio in grams per liter of glyphosate acid equivalent to Silwet L-77 to surfactant. All of the formulations in Table 1 showed acceptable stability in one week at -5 C and *ooo oo S. a a a. a.

*5 a. ease *5 a..aa* S S *a* 0 a 0W S. 0 Table 1 Example Active composition (g/1) Chemical Name of Surfactant No.

lauryl dimethyl amine oxide ditto Glyphosate SILWET L-77 Surf actant Dipropylene Water Glyphosate SILWET L-77 Surf actant Water Glyphosate SILWET L-77 Surf actant Water 180 17 remaining 180 100 remaining 115 310 380 Glycol remaining ditto ditto Glyphosate 360 SILWET L-77 34 MON 0818 170 Surf actant Polyethylene glycol #400 Water remaining 09-21(2579)A This invention also includes a method of killing or controlling weeds by applying a herbicidally effective amount of the composition of this invention to the locus of the plant or weed to be killed or controlled.

Dilution with water before application to the locus of the plant or weed is desirable, although perhaps not necessary in all cases. In general when killing or controlling weeds or plants using this invention, the methods of use generally disclosed in U.S. Patent 3,799,458 for salts and compositions employing N-phosphonomethylglycine and the other patents referred to hereinabove will be useful to those of skill in the art.

The application of an effective amount of the herbicidally effective compounds used in the compositions of this invention to the plant is essential for the practice of the present invention. The exact amount of herbicide containing N-phosphonomethylglycine as the active ingredient to be employed is dependent upon the response desired in the plant, as well as such other factors as the plant species and stage of development thereof, and the amount of rainfall, as well as the specific salt employed. In foliar treatment for the e; control of vegetative growth, the active ingredients are applied in amounts from about 0.01 to about 20 or more pounds per acre. In applications for the control of aquatic plants, the active ingredients are applied in amounts of from about 0.01 parts per million to about 1000 parts per million, based on the aquatic medium. An 30 effective amount for phytotoxic or herbicidal control is that amount necessary for overall or selective control, I. i.e. a phytotoxic or herbicidal amount. It is believed that one skilled in the art can readily determine from the teachings of this specification, and patents 35 referred herein the approximate application rate.

Granules may also 'e applied using conventional broadcast techniaues.

Claims

1. A storage stable, aqueous composition, comprising effective amounts of at least one glyphosate based herbicide, a silicone copolymer wetting agent and an amphuteric surfactant.

2. The composition of Claim 1 wherein the surfactant is an ;rline oxide.

3. The composition of Claim 2 wherein the amine oxide is selected from a trialkylamine oxide, dihydroxyethyl alkyl amine oxide, di(polyhydroxyethylene) alkyl amine oxide, and loweralkyl polyoxyethylene alkyl amine oxide.

4. The composition of Claim 3 wherein: a) the trialkylamine oxide is i) %auryl dimethyl amine oxide, or ii) stearyl dimethyl amine oxide; b) the dihydroxyethyl alkyl amine oxide is 15 i) dihydroxyethyl octyl amine oxide, or ii) dihydroxyethyl dodecyl amine oxide, or iii) dihydroxyethyl tallowamine oxide; c) the di(polyhydroxyethylene) alkyl amine oxide is a. i) bis(polyoxyethylene) tallowamine oxide; or d) the loweralkyl polyoxyethylene alkyl amine oxide is i) methyl polyoxyethylene mole) cocoamine oxide.

The composition of any one of Claims 1 to 4 wherein S" said wetting agent is a silicone copolymer having the formula R R R R I I I I R (I) R R R R x _y R 1 0 C 2 H 3 R C 3 Hg0 b R where each R is independently a monovalent hydrocarbyl radical, R 1 is a divalent hydrocarbylene radical, R 2 is independently hydrogen or a lower hydroxyalkyl radical, R 3 is hydrogen or a monovalent hydrocarbyl radical, and x, y, a and b are integers independently greater than or equal to zero.

6. The composition of Claim 5 wherein R and R 3 are -CH 3 R 1 is -C 3 H 6 R 2 is hydrogen, x is zero or one, y is one to five, a is five to twenty and b is zero.

7. The composition of Claim 5 wherein R and R 3 are -CH 3 R 2 is hydrogen, a is five to twenty and b is zero.

8. The composition of Claim 5 wherein said wetting agent is L-77.

9. The composition of any one of Claims 1 to 8 wherein 15 said glyphosate is in the form of the isopropylamine s?-t of glyphosate.

10. The composition of any one of Claims 1 to 9 wherein the weight percent glyphosate is in the range from 5 to 35, the weight percent silicone copolymer wetting agent is in the range 20 from 0.1 to 50, and the percent amphoretic surfactant is in the weight range from 1 to

11. The composition of Claim 10 wherein the weight percent silicone copolymer wetting agent is in the range from 1 to *oeIT -13-

12. The composition of Claim 10 wherein the weight percent amphoretic surfactant is in the range from 5 to

13. The composition of Claim 10 wherein the weight percent silicone copolymer wetting agent is in the range from 1 to and the weight percent amphoretic surfactant is in the range from 5 to

14. A method of killing or controlling weeds by applying the composition of any one of Claims 1 to 13 to the weed to be killed or controlled. DATED this Ist day of February, 1995 MONSANTO COMPANY, By its Patent Attorneys, S. -W-E-L-N-G-TON-& VO S. Wellington) 0*00 0000 0000 00 0 0 0 000 0 0 0 0 000 0 0 0 0 0 *D 0 0 0 0 0 0 0000 A/RR/3346/3 09-21(2579)A ABSTRACT This invention relates to a storage stable aqueous formulation, agriculturally acceptable glyphosate herbicide composition, to a method of use for killing or controlling weeds and to a process for preparing such compositions. too: 0 o 0 0 0 ee* S* 0 0 00 0 0